Bis(phenyltolyl) ethers and method of manufacture



ip-W j United States Patent 3,178,480 BIS(PHENYLTOLYL) ETHERS AND METHOD OF MANUFACTURE 1 James D. Doedens, Midland, Howard P. Cordts, Bay City,

and David F. Wisniewski, Auburn, Mich., assignors to The Dow Chemical Company, Midland, Mich., a corporation of Delaware No Drawing. Filed Aug. 31, 1959, Ser. No. 836,927

4 Claims. (Cl. 260-612) This invention concerns new chemical compositions which are liquid condensation products of a benzenoid hydrocarbon having up to two alkyl substituents containing from 1 to 2 carbon atoms with 4,4-di(chloromethyl) diphenyl oxide, hereinafter abbreviated as DCMDPO. It also concerns their method of manufacture.

The new compounds of this invention are unusually effective as adsorbents in chromatography, particularly vapor phase chromatography.

The products of this invention are prepared by a condensation or alkylation in the presence ofa Friedel-Crafts catalyst, e.g., ZnCl FeCl BF etc., involving two moles of benzenoid hydrocarbon per mole of DCMDPO when the dialkyl benzenes are coreactants, 3 moles of benzenoid hydrocarbon per two moles of DCMDPO when benzene is the coreactant and a mixed condensate of 2 and 3 moles of benzenoid hydrocarbon per 1 and 2moles of DCMDPO 1 when a monoalkylbenzene is the coreactant. For example,

bis(ot-x-xylyl-p-tolyhether is produced when 2 molar proportions of xylene are condensed with one mole of DCMDPO, x representing a position on the benzene nucleus, oc,ot'-blS( (p-( a-phenyl-p-tolyloxy) phenyl) )-p-xylene is produced when 3 moles of benzene are condensed with 2 moles of DCMDPO, a mixture of approximately 70 weight percent of bis(ot-x-tolyl-p-tolyl)ether and, approximately 30 percent 2-methyl-1,4-bis((p-(a-x-tolyl-p-tolyloxy) benzyl)) benzene is produced when toluene present in excess is condensed with DCMDPO,'and' a mixture of the analogous ethyl homologs, approximately 70 weight percent bis(a-x-ethylphenyl p tolyl)ether and approximately 30 percent 2-ethyl-1,4-bis((p-(a-x-ethylphenyl-pto1yloxy)benzyl)) benzene is produced when ethylbenzene present in excess is condensed with DCMDPO. The ethylbenzene and toluene condensation products have mainly para-substitution with a small amount of ortho-substitution. The xylene condensate has mainly 1,2,4-substitution with a small amount of 1,2,3- and 1,2,6-substitution. The indicated positions are those of the alkyl substituents of the benzenoid hydrocarbon moieties relative to the 4,4'-di methylene diphenyl oxide moieties, hereinafter referred to as diphenyl oxide moieties.

The reaction is carried out by reacting the benzenoid hydrocarbon, present in stoichiometric excess over the DCMDPO, e.g., more than 2 moles of the former to one of the latter, and suflicient in any event to dissolve all of the DCMDPO at reaction temperature in the presence of a small catalytic amount of a Friedel-Crafts catalyst, generally from a trace up to 2 weight percent, DCMDPO basis. A simple trial suflices to determine the amount of benzenoid hydrocarbon sufficient to dissolve the DCMDPO. A reaction temperature between 45 C. and the boiling point of the benzenoid hydrocarbon, generally between 50 and 150 C. and preferably at the boiling point of the benzenoid hydrocarbon reactant is used. Excess benzenoid hydrocarbon acts as a moderating diluent, also expedites reaction in accordance with Le Chateliers law and, further, prevents self-condensation of the DCMDPO. The reaction is carried out until hydrogen chloride evolution has stopped. At lower temperatures, as expected, longer reaction times are required. But no effect on yield is noted at any point within the operable ice reaction temperature range provided sufficient time is allowed for all of the hydrogen chloride to be evolved.

The liquid products referred to herein were identified by infrared analysis together with molecular weight determinations.

The DCMDPO can be prepared by the method of Tomita et al., Jl. Pharm. Soc. Jap. 70:44 (1950).

The following examples are in illustration of the invention and not in limitation thereof. Parts and percentages therein are by weight.

EXAMPLE I.REACTION OF DCMDPO WITH XYLENE Charge:

107 g. (0.4 mol) DCMDPO 856 g. (8.07 mols) xylene 4 g. zinc chloride The above reactants were charged [to a 2-liter 3-necked pot equipped with a mechanically driven agitator and two reflux condensers. Heat was applied gradually to 74 C., at which temperature HCl was evolved vigorously. When the HCl evolution had slowed down, the temperature was increased to 135 C. and was held there for 10 hours. The reaction mixture was then cooled and transferred to a separatory funnel wehre it was washed twice with water, once with aqueous 5 percent NaHCO solution, and again with water. After the final separation, the mixture was filtered and stripped to 120 C. at 25 mm. Hg to rid it of xylene. The residue was then transferred to another still and stripped of solvent to a pot temperature of 270 C. at 0.7 mm. Hg. A quantity of 127 g. liquid product was recovered for a 779.5 percent yield, DCMDPO basis, identified as bis(a-x-xylyl-p-tolyl) ether by infrared analysis and a molecular weight of 400 (calcd. 406).

EXAMPLE 2.REACTION OF DCMDPO WITH ETHYLBENZENE Charge:

' 107 g. (0.4 mole) DCMDPO 862 g. (8.07 moles) ethylbenzene 4 g. zinc chloride The procedure of Example 1 was repeated. The washed, filtered organic phase was stripped to 250 C. at 0.7 mm. Hg to remove ethylbenzene. A quantity of g. liquid product was recovered for a 71 precent yield. It was identified as a mixture of approximately70 weight percent bis(u-x-ethylphenyl-p-tolyl) ether and approximately 30 percent 2-ethyl-1,4-bis((p-(a-x-ethylphenyl-p-tolyloxy) benzyl)) benzene by infrared analysis and a molecular weight of 500 (calcd. for 70:30 mixture, 497).

EXAMPLE 3.REACT ION OF DCMDPO WITH TOLUENE cent sodium bicarbonate solution, and again with water until the aqueous phase was neutral. The excess toluene and any Water was stripped off at a temperature of 250 C. at 2 mm. Hg. Liquid product amounting to 690 g. was identified as a mixture of ca. 70 weight percent bis- (a-x-tolyl-p-tolyl) ether and ca. 30 percent 2-methyl-1,4- bis( (p-(a-x-tolyhp-tolyloxy)benzyl)) benzene by infrared 3 analysis and by a molecular Weight of 458 (calculated for 70:30 mixture, 462).

EXAMPLE 4.REACTION OF DCMDPO WITH BENZENE A quantity of 1.87 moles (500 g.) DCMDPO was dissolved in 1500 g. (19.2 moles) benzene. To this solution was added 30 g. aluminum chloride catalyst. The reaction mixture was heated to reflux in a 2-liter 3-necked flask equipped with a reflux condenser, thermometer and mechanical agitator. The reaction mixture was held at 60-65 C. for 2 hours, after which no more HCl evolution was noted. It was then cooled to 50 C. and poured into chilled water. The organic layer was separated, Washed with water, with aqueous percent NaHCO solution and again with Water. The benzene was then stripped off to a pot temperature of 200 C. A quantity of 629 g. liquid product was recovered for a 96.1 percent yield based on DCMDPO. The product was identified as 71,01- bis((p-(a-phetnyl-p-tolyloxy)phenyl))-p-xylene by infrared analysis and by a molecular weight of 611 (calculated 620).

EXAMPLE 5 The following table illustrates the value in adsorption chromatography of a mixture of about 70 weight percent of bis(a-x-to1yl-p-tolyl) ether and about Weight percent of 2-methyl-1,4-bis( (p-(a-x-tolyl-p-tolyloxy) benzyl)) benzene loaded on a column of diatomaceous earth, a conventional particulate inert packing material. In general, the data are presented similarly to the presentation of Scholly and Brenner, Proceedings 1959, 2d Biannual International Gas Chromatography Symposium, pp. 111- 140, Instrument Society of America, 313 Sixth Avenue, Pittsburgh 22, Pa., 1959, except that instead of giving the time in minutes for a component species to emerge, there is given the retention volume, R of the gas corrected to 760 mm. and 0 C.

Table I Conditions employed Inlet pressure=15.1 cm. Hg in all cases helium gas) Flow (ml./min.)=29.1 at 997 C., 31 at 79.7C., 35.6

at 55.8C., and 41.5 at 24.7 C. Weight of stationary liquid phase on column 13.2 g. Length and diameter of column 288 cm. x 0.6 cm.

Rv values at various temperatures Com ound p 13.1. Rv (ml./ Rv/Rv 0.) Temp. min. (pentane) corr.)

Saturated paraflins: 99 7 49 1 00 Pentme i 211 7 280 1100 99.7 102 2. 09 7 i 5 s 2 Heptami 79. 7 371' 5.12 Octane 125. 7 99. 7 406 8. Unsaturated and branched paraflms: 99 7 51 1 04 Pentene-l 30.0 322 99.7 64 1.31 cls-Pentene-Z 36. 9 99.7 35 0.71 2 n1ethyl butane 27. 9 24. 7 192 Z-methyl-l-butene 31. 2 22:; 22 28 2-methyl-1,3-butadiene 34.1 Halogenated paraifins:

Methylene chloride 4o. 0 g: Chloroform 61.3 3; Carbon tetrachloride 76.7 g: Ethylbromlde. 38. 4 99.7 140 2.84 n-Propylbromide 71. 0 99. 7 306 6. 17 iso-Propylbroml 59. 4 99. 7 201 4. O8 n-Butylbromide 101. 6 99.7 634 12. 9 isO-Butylbrormd 91. 4 99. 7 468 9. 51 sec-Butylbromide 91. 2 99. 7 450 9. 18 Alicyclic Hydrocarbons: 1 3

Cyclopentane 49. 3 22:; i g: 3 Cyclohexane 80. 7 $81; 2%; g: g? Methylcyclohexane 100. 9 99.7 371 7. 63

Table 1--Conti'nued RV values at various temperatures Com ound p B.P. Rv 1111 Rv/Rv 0.) Temp. min. (pentane) eorr.)

Aromatic: 44 20 Benzene 80. 1 38:; 2 1 Toluene 6 $37 1,322 $21? Ethylbenzene 136. 2 g i o-Xylene 144. 4 99. 7 2, 500 60. a m-Xylene. 139. 1 99.7 2, 067 41. 5 p-Xylene 138. 4 99. 7 1, 984 40. 1

Heterocyclic: 99 7 5 6 u 5 Thmphene i 7917 1, 020 1419 -d xa e 101.4 33;; 1, Egg

Alcohols: Methanol 64. 7 1:?2 m a; 122 132 n-Propan0l '97. 2 99. 7 207 4. 26 lso-Propauol. 82. 4 99. 7 114 2; 32 11-Butan0l... 118. 0 99. 7 447 9. l6 isO-ButanOL 108. 0 99. 7 309 0. 32 sec-ButanoL 99. 5 99. 7 253 5. 15 tertButan0l 82. 9 99.7 129 2. 63 iso-Amyl alcohol. 132. 0 99. 7 742 15. 1

E tsee-Amyl alcohol 119. 9 99.7 478 9. 74

s ers:

Ethyl acetate 77.1 2: n-Propyl acetate 101. 6 33:; 328 3 K tn-Butyl acetate 126. 1 99. 7 1, 141 23.2

e ones:

99.7 149 3.01 Acetone 56. 1 55' 8 468 88 Methyl ethyl ketone 79.6 g: Methyl propyl ketone--. 102. 4 99. 7 566 11.4

Aldehydes: 73 1 45 Acetaldehyde 20.2 32:; 446 62 Propionaldehyde 48. 8 g: g

EthButryaldehyde. 74. 7 99.7 284 5. 74

ers:

4 99. 7 74 1. 53 methyl 3 24.7 594 2.15 259 5.31 'p py 1 4 9 47 What is claimed is: 4 1. A compound having the general formula wherein -CH C H O--C H CH represents a his- (p-tolyl)ether moiety, --C l-I represents a benzene moiety, R R and R individually represent one of the group consisting of hydrogen and alkyl groups having from 1 to 2 carbon atoms, at least one of which is hydrogen, and n is an integer from 1 to 2, said compound being a liquid.

2. Bis(a-x-xy1yl-p-tolyl) ether.

3. oc,a'-B1S (p-(u-phenyl-p-tolyloxy)phenyl) p-xylene.

4. A method for making liquid condensation products of 4,4'-di(chloromethyl)diphenyl oxide and a benzenoid hydrocarbon having the formula R R R C H wherein C H represents a benzene moiety and R R and R individually represent one of the group of hydrogen and alkyl groups having from 1 to 2 carbon atoms and at least one of which is hydrogen, said condensation products having from 1 to 2 diphenyl oxide moieties and from 2 to 3 benzenoid hydrocarbon moieties per molecule, which method comprises reacting a homogeneous solution of 4,4'-di(chloromethyl) diphenyl oxide in an excess of said benzenoid hydrocarbon suflicient to dissolve the 4,4- di(chloromethyl)diphenyl oxide at reaction temperature and containing more than 2 moles of benzenoid hydrocarbon per mole of 4,4-di(chloromethyl) diphenyl oxide at a temperature between about 45 C. and the boiling point of said benzenoid hydrocarbon in the presence of a Friedel-Crafts catalyst until hydrogen chloride evolution ceases.

References Cited by the Examiner UNITED STATES PATENTS 6 Hess et a1. 252-428 Horsley et a1. 260-613 Doedens 260-613 Doying 252-428 LEON ZITVER, Primary Examiner.

JULIUS GREENWALD, CHARLES E. PARKER,

Examiners. 

1. A COMPOUND HAVING THE GENERAL FORMULA 